EP3003042B1 - Composés hétérocycliques en tant que moyen de lutte contre les parasites - Google Patents

Composés hétérocycliques en tant que moyen de lutte contre les parasites Download PDF

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Publication number
EP3003042B1
EP3003042B1 EP14726141.6A EP14726141A EP3003042B1 EP 3003042 B1 EP3003042 B1 EP 3003042B1 EP 14726141 A EP14726141 A EP 14726141A EP 3003042 B1 EP3003042 B1 EP 3003042B1
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Prior art keywords
alkyl
substituted
halogen
cyano
alkoxy
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EP3003042A1 (fr
Inventor
Silvia Cerezo-Galvez
Thomas Bretschneider
Reiner Fischer
Martin FÜSSLEIN
Christoph Grondal
Peter Jeschke
Peter Reinisch
Mehmet GUECLUE
Kerstin Ilg
Peter Lösel
Olga Malsam
Arnd Voerste
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Bayer CropScience AG
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Bayer CropScience AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A61P33/10—Anthelmintics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A61P33/14—Ectoparasiticides, e.g. scabicides

Definitions

  • the present application relates to the non-therapeutic use of known and novel heterocyclic compounds for controlling animal pests, novel heterocyclic compounds, processes for their preparation and their use for controlling animal pests.
  • WO 2012/102387 A1 Heterocyclic compounds are described which can be used in particular as insecticides and acaricides.
  • Heterocyclic compounds for pharmaceutical applications are in WO 2004/009597 A2 .
  • WO 2008/107418 A1 WO 2009/068617 A1 and US 2004/242596 A1 disclosed.
  • the object of the present invention was to provide compounds which broaden the spectrum of pesticides from various aspects.
  • the compounds of the formula (I) according to the invention can be represented by the formulas (Ia) and (Ib).
  • Halogen selected from the group fluorine, chlorine, bromine and iodine, preferably again from the series fluorine, chlorine and bromine
  • Aryl also as part of a larger unit, such as, for example, arylalkyl selected from the group consisting of phenyl, naphthyl, anthryl, phenanthrenyl and in turn preferably represents phenyl, Hetaryl (equivalent to heteroaryl, also as part of a larger moiety such as hetarylalkyl) selected from the series furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl , Thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,
  • Halogen selected from the group fluorine, chlorine, bromine and iodine preferably again from the series fluorine, chlorine and bromine
  • Aryl also as part of a larger unit, such as, for example, arylalkyl
  • arylalkyl selected from the group phenyl, naphthyl, anthryl and phenanthrenyl and in turn preferably represents phenyl
  • Hetaryl also as part of a larger unit, such as hetarylalkyl
  • Hetaryl also as part of a larger unit, such as hetarylalkyl
  • Hetaryl also as part of a larger unit, such as hetarylalkyl
  • Hetaryl also as part of a larger unit, such as hetarylalkyl
  • Heterocyclyl selected from azetidinyl, azolidinyl, azinanyl, oxetanyl, oxolanyl, oxany
  • Halogen is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine.
  • Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl
  • heteroatoms e.g. in alkoxy, as far as possible, in each case straight-chain or branched.
  • optionally substituted radicals may be monosubstituted or polysubstituted, with multiple substituents the substituents being the same or different.
  • Very particularly preferably used according to the invention are compounds of the formula (I) which contain a combination of the meanings given above as being very particularly preferred.
  • a preferred embodiment of the invention relates to compounds of the formula (Ia).
  • Another preferred embodiment of the invention relates to compounds of the formula (Ib).
  • Another preferred embodiment of the invention relates to compounds of the formula (Ia) in which Het is 3-pyridyl.
  • Another preferred embodiment of the invention relates to compounds of the formula (Ib) in which Het is 3-pyridyl.
  • Another preferred embodiment of the invention relates to compounds of the formula (Ib) in which Q is C-H.
  • the compounds of the formula (I) may also be present in different compositions as stereoisomers, ie as geometric and / or optical isomers or mixtures of isomers. Both the pure stereoisomers and any mixtures of these isomers are the subject of this invention, although in general only compounds of the formula (I) are mentioned here.
  • optically active stereoisomeric forms of the compounds of the formula (I) and salts thereof are used according to the invention.
  • the invention therefore relates to both the pure enantiomers and diastereomers, as well as their mixtures for controlling animal pests, which include arthropods and in particular insects.
  • Halogen selected from the group fluorine, chlorine, bromine and iodine, preferably again from the series fluorine, chlorine and bromine
  • Aryl also as part of a larger unit, such as, for example, arylalkyl selected from the group consisting of phenyl, naphthyl, anthryl, phenanthrenyl and in turn preferably represents phenyl, Hetaryl (equivalent to heteroaryl, also as part of a larger moiety such as hetarylalkyl) selected from the series furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl , Thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,
  • Halogen selected from the group fluorine, chlorine, bromine and iodine, preferably again from the series fluorine, chlorine and bromine
  • Aryl also as part of a larger unit, such as, for example, arylalkyl
  • arylalkyl selected from the group consisting of phenyl, naphthyl, anthryl, phenanthrenyl and in turn preferably represents phenyl
  • Hetaryl also as part of a larger unit, such as hetarylalkyl selected from the series pyridyl, pyrimidyl, pyrazanyl, thiazolyl, isothiazolyl and pyridazinyl.
  • Halogen is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine.
  • Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl
  • heteroatoms e.g. in alkoxy, as far as possible, in each case straight-chain or branched.
  • optionally substituted radicals may be monosubstituted or polysubstituted, with multiple substituents the substituents being the same or different.
  • Halogen selected from the group fluorine, chlorine, bromine and iodine, preferably again from the series fluorine, chlorine and bromine
  • Aryl also as part of a larger unit, such as, for example, arylalkyl selected from the group consisting of phenyl, naphthyl, anthryl, phenanthrenyl and in turn preferably represents phenyl, Hetaryl (equivalent to heteroaryl, also as part of a larger moiety such as hetarylalkyl) selected from the series furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl , Thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,
  • Halogen selected from the group fluorine, chlorine, bromine and iodine preferably again from the series fluorine, chlorine and bromine
  • Aryl also as part of a larger unit, such as, for example, arylalkyl
  • arylalkyl selected from the group phenyl, naphthyl, anthryl and phenanthrenyl and in turn preferably represents phenyl
  • Hetaryl also as part of a larger unit, such as hetarylalkyl
  • Hetaryl also as part of a larger unit, such as hetarylalkyl
  • Hetaryl also as part of a larger unit, such as hetarylalkyl
  • Hetaryl also as part of a larger unit, such as hetarylalkyl
  • Heterocyclyl selected from azetidinyl, azolidinyl, azinanyl, oxetanyl, oxolanyl, oxany
  • Halogen is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine.
  • Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl
  • heteroatoms e.g. in alkoxy, as far as possible, in each case straight-chain or branched.
  • optionally substituted radicals may be monosubstituted or polysubstituted, with multiple substituents the substituents being the same or different.
  • novel compounds of the formula (I) can be prepared by the processes described below.
  • the compounds of the formula (Ia) and (Ib) can be prepared, for example, according to process A in two steps, as shown in the following scheme.
  • the aminopyrazoles of the formulas (IIIa) and (IIIb) required therefor can be prepared, for example, by processes B, C and D.
  • Het, Q, R 1 and R 2 have the meanings given above
  • R ' is hydrogen or alkyl (in particular methyl and ethyl)
  • Hal is halogen (preferably chlorine, bromine and iodine)
  • PG is a suitable protective group.
  • compounds of the formulas (IIIa) or (IIIb) can be converted by various methods to give carboxamides of the formulas (IIa) or (IIb).
  • R ' alkyl
  • this reaction can take place without activation (cf. BM Trost and I. Fleming in Comprehensive Organic Synthesis, Ed. Pergamon, 1991, Vol. 6 ).
  • activation methods by the formation of an aluminum amide are known in the literature (see T. Ooi and K. Marouka in Science of Synthesis, Ed. Georg Thieme, 2003, Vol. 7, 225-246 ).
  • Aluminum amides can be prepared, for example, from the amines or their salts by reaction with trimethylaluminum or their air-stable adduct with 1,4-diazobicyclo [2.2.2] octane (DABCO) (cf. S. Woodward in Tet. Lett. 2006, 47, 5767-5769 ).
  • DABCO 1,4-diazobicyclo [2.2.2] octane
  • an inorganic base preferably sodium hydroxide and potassium hydroxide
  • an inert organic solvent optionally by acidification with a dilute acid (eg aqueous hydrochloric acid)
  • a dilute acid eg aqueous hydrochloric acid
  • amidation reactions are carried out in the presence of a condensing agent, optionally in the presence of an acid acceptor and optionally in the presence of a solvent.
  • Suitable condensing agents are all condensing agents customarily used for such amidation reactions. Examples which may be mentioned are acid halide formers such as phosgene, phosphorus trichloride, oxalyl chloride or thionyl chloride; Carbodiimides, such as N, N'-dicyclohexylcarbodiimide (DCC) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide (EDCI), or other conventional condensing agents , such as phosphorus pentoxide, polyphosphoric acid, N, N'- carbonyldiimidazole, 2-chloropyridine 1-Methoiodide (Mukaiyamas reagent), 2-ethoxy-N-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ), triphenylphosphine / carbon tetrachloride, bromotripyrrolidino-phosphonium
  • Suitable acid acceptors are all customary inorganic or organic bases, for example triethylamine, diisopropylethylamine, N- methylmorpholine or N, N- dimethylaminopyridine. If appropriate, process A according to the invention is carried out in the presence of a suitable reaction auxiliary, for example N, N- dimethylformamide or N, N- dimethylaminopyridine.
  • Suitable solvents or diluents are all interten organic solvents, for example aliphatic or aromatic hydrocarbons (such as petroleum ether, toluene), halogenated hydrocarbons (such as chlorotoluene, dichloromethane, chloroform, 1,2-dichloroethane), ethers (such as diethyl ether, dioxane, tetrahydrofuran , 1,2-dimethoxyethane), esters (such as ethyl acetate or methyl ester), nitrohydrocarbons (such as nitromethane, nitroethane, nitrobenzene), nitriles (such as acetonitrile, benzonitrile), amides (such as N, N- dimethylformamide, N, N- dimethylacetamide , N- methylformanilide, N- methylpyrrolidone, hexamethylphosphoric triamide) and dimethyl sulfoxide or water or mixture
  • the carboxylic acid amides of the formulas (IIa) or (IIb) can be cyclized to the compounds of the formulas (Ia) or (Ib).
  • the pyrazolopyrimidinones of the formulas (Ia) or (Ib) can be prepared by azodiazotization of the carboxamides of the formulas (IIa) or (IIb) by methods known from the literature.
  • compounds of formulas (IIa) and (IIb) are added at 0 to 5 ° C with a nitrite source, such as sodium nitrite or isobutyl nitrite, typically in water, alcohol or a polar, inert solvent and in the presence of an organic or inorganic acid.
  • a nitrite source such as sodium nitrite or isobutyl nitrite
  • aminopyrazoles of the formulas (IIIa) and (IIIb) required in process A can be prepared, for example, by processes B, C and D.
  • Aminopyrazoles of the formulas (IIIa) and (IIIb) can be prepared in one step, for example by means of an Ullmann reaction, by methods known in principle (cf. Chem. Rev. 2008, 108, 3054-3131 ) are prepared from the corresponding bromides of the formula (IV) and the aminopyrazoles of the formula (V).
  • Examples of the arylation of aminopyrazoles are in WO2007 / 039146 described.
  • copper (I) -based catalysts eg, copper (I) iodide
  • a base eg, potassium carbonate
  • a ligand eg, trans- 1,2-diaminocyclohexane or trans - N, N ' -Dimethyl-1,2-cyclohexanediamine
  • a suitable solvent eg, dioxane, N, N- dimethylformamide, N, N- dimethylacetamide or pyridine
  • Temperatures between 80 and 180 ° C are usually needed for the reaction.
  • each can be used for these reactions suitable, commercially available microwave apparatus are used (eg Anton Paar Monowave 300, CEM Discover S, Biotage initiator 60).
  • aminopyrazoles of the formulas (IIIa) and (IIIb) thus prepared can be separated, for example by means of chromatographic separation over silica gel or RP (C-18) or by stirring or recrystallization using suitable solvents.
  • aminopyrazoles of the formula (IIIa) can be prepared by methods known in principle from hydrazines of the formula (VI) or salts thereof (preferably hydrochlorides). For example, according to Robins' syntheses in J. Amer. Chem. Soc. 1956, 78, 784-790 or after J. Med. Chem. 2005, 48, 5162-5174 by reacting at a temperature between 50 ° C and 100 ° C with a suitable cyano compound of the formula (IX) in which R and R "are alkyl (preferably methyl and ethyl), optionally in an inert organic solvent (eg alcohols).
  • a suitable cyano compound of the formula (IX) in which R and R "are alkyl (preferably methyl and ethyl), optionally in an inert organic solvent (eg alcohols).
  • aminopyrazoles of the formula (IIIb) can be prepared by methods known from the literature from hydrazines of the formula (VI) or salts thereof (preferably hydrochlorides) (cf. EJ Med. Chem. 2011, 46, 3867-3876 ).
  • step 1 the hydrazine of the formula (VI) is protected, for example by reaction with an aldehyde (typically benzaldehyde, cf. Bioorg. Med. Chem. Let 2004, 14, 4585-4589 ) to form a hydrazone.
  • the protected compound of the formula (VII) can be reacted with a cyano derivative of the formula (IX) to give compounds of the formula (VIII) (cf. J. Het. Chem. 1990, 27, 1805-1807 ), typically in an inert organic solvent (eg, an alcohol) at a temperature between 50 ° C and 100 ° C (step 2).
  • an acid eg hydrochloric acid
  • Heterocyclic hydrazines of the formula (VI) are commercially available or can be prepared by literature methods from the corresponding halides of the formula (IV), for example as described in US Pat WO 2010/015849 for various heterocycles described: by reaction with hydrazine hydrate, optionally in an inert organic solvent (eg ethanol), at temperatures between 60 and 120 ° C; or by reaction with di- tert- butyl-hydrazodicarboxylate and subsequent cleavage of the tert- butylcarboxylate groups by reaction with an acid (typically hydrochloric acid in an organic solvent such as dioxane, also with trifluoroacetic acid), which leads to the formation of the corresponding salts.
  • an acid typically hydrochloric acid in an organic solvent such as dioxane, also with trifluoroacetic acid
  • hydrazines of the formula (VI) 3-hydrazinylpyridine, 5-hydrazinylpyrimidine, 4-Hydrazinylpyridazin.
  • Cyano compounds of the formula (IX) can be prepared from cyanoacetic acid alkyl esters (preferably methyl ester and ethyl ester) by methods known from the literature.
  • N- substitution of the pyrazolopyrimidinones of the formulas (Ia-H) or (Ib-H) can be carried out in different ways.
  • the reaction is carried out in the presence of a base, often carbonate or phosphate bases, such as potassium carbonate, sodium carbonate, cesium carbonate or potassium phosphate, in suitable solvents such as dioxane, toluene, dimethyl sulfoxide or N, N- dimethylformamide. It can also additives such.
  • potassium iodide cesium fluoride or other salts.
  • such reactions can be carried out under palladium catalysis, for example by using catalysts such as palladium acetate, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium (II) chloride, tris (dibenzylideneacetone) dipalladium (0) in the presence of ligands , for example 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl, 9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene, 1,1'-bis (diphenylphosphino) - ferrocene, and bases such as potassium carbonate, sodium carbonate, cesium carbonate or potassium phosphate, in suitable solvents such as dioxane, toluene, dimethyl sulfoxide or N, N- dimethylformamide.
  • catalysts such as palladium acetate, tetraki
  • compounds of the formulas (Ia) or (Ib) can alternatively be prepared by reacting suitable boronic acids with the pyrazolopyrimidinones of the formulas (Ia-H) or (Ib-H).
  • the reactions find catalysis or mediation by copper (II) salts such as copper (II) acetate, copper (II) triflate or by copper (I) salts such as copper (I) chloride , Copper (I) acetate under air or oxygen atmosphere, often under dehydrating conditions (for example in the presence of molecular sieve) instead.
  • Suitable bases are triethylamine, N- ethyldiisopropylamine, pyridine, 2,6-lutidine, N- methylmorpholine or 1,8-diazabicycloundec-7-ene in suitable solvents such as, for example, dichloromethane, dichloroethane, methanol, N, N- dimethylformamide, Tetrahydrofuran, dioxane, acetonitrile, ethyl acetate or toluene used. Numerous examples are described in the literature, including in WO 2008/062905 or in WO 2009/133970 for pyrimidinones. Summary overviews can be found in Synthesis 2011, no.
  • boron compounds such as potassium trifluoroborates, boronic acid esters, etc., as well as other organometallic compounds such as stannanes, silanes or bismuthans can be used instead of boronic acid.
  • novel compounds of the formula (I) have pronounced biological properties and, above all, for controlling animal pests, in particular insects, arachnids and nematodes, which are used in agriculture, in forestry, in the protection of stored products and materials, and on the hygiene sector are suitable.
  • arachnids e.g. Acarus siro, Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp.
  • Eriophyes spp. Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp. Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici.
  • Gastropoda e.g. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.
  • helminths e.g. Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Ne
  • protozoa such as Eimeria
  • Eimeria protozoa
  • Heliopeltis spp. Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., Psallus seriatus, Pseudacysta persea, Rhodnius spp. Sahlbergella singularis, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.
  • Stictocephala festina Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes vaporariorum, Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitif OLII.
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • Orthoptera e.g. Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.
  • siphonaptera e.g. Ceratophyllus spp., Xenopsylla cheopis.
  • Symphyla e.g. Scutigerella immaculata.
  • Thysanoptera e.g. Basothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.
  • Thysanura e.g. Lepisma saccharina.
  • the plant parasitic nematodes include e.g. Anguina spp., Aphelenchoides spp., Belonoaimus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp., Heliocotylenchus spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Rotylenchus spp. Trichodorus spp., Tylenchorhynchus spp., Tylenchulus spp., Tylenchulus semipenetrans, Xiphinema spp.
  • Anguina spp. Aphelenchoides spp., Belonoaimus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera
  • the compounds according to the invention can also be used in certain concentrations or application rates as herbicides, safeners, growth regulators or agents for improving plant properties, or as microbicides, for example as fungicides, antimycotics, bactericides, viricides (including anti-viral agents) or as anti-MLO agents (Mycoplasma -like-organism) and RLO (Rickettsia-like-organism). They can also be used as intermediates or precursors for the synthesis of other active ingredients.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, scattering granules, suspension-emulsion concentrates, active substance-impregnated natural substances, active substance-impregnated synthetic Substances, fertilizers and microencapsulation in polymeric substances.
  • customary formulations such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, scattering granules, suspension-emulsion concentrates, active substance-impregnated natural substances, active substance-impregnated synthetic Substances, fertilizers and microencapsulation in polymeric substances.
  • formulations are prepared in a known manner, e.g. by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents.
  • extenders ie liquid solvents and / or solid carriers
  • surface-active agents ie emulsifiers and / or dispersants and / or foam-forming agents.
  • Excipients which can be used are those which are suitable for imparting special properties to the composition itself and / or preparations derived therefrom (for example spray liquor, seed dressing), such as certain technical properties and / or specific biological properties.
  • Typical auxiliaries are: extenders, solvents and carriers.
  • polar and non-polar organic chemical liquids e.g. from the classes of aromatic and non-aromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), alcohols and polyols (which may also be substituted, etherified and / or esterified), ketones (such as acetone, cyclohexanone), Esters (including fats and oils) and (poly) ethers, simple and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide).
  • aromatic and non-aromatic hydrocarbons such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes
  • alcohols and polyols which may also be substituted, etherified and / or esterified
  • ketones such
  • Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g.
  • Petroleum fractions mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethyl sulfoxide, and water.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids may be used in the formulations.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • inorganic pigments e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • additives may be fragrances, mineral or vegetable optionally modified oils, waxes and nutrients (also trace nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • Stabilizers such as cold stabilizers, preservatives, antioxidants, light stabilizers or other chemical and / or physical stability-improving agents may also be present.
  • the formulations generally contain between 0.01 and 98% by weight of active ingredient, preferably between 0.5 and 90%.
  • the active compounds according to the invention can also be mixed with one or more suitable fungicides, bactericides, acaricides, nematicides, insecticides, microbicides, fertilizers, attractants, sterilants, synergists, safeners, Semiochemicals and / or plant growth regulators can be used, for example, to broaden the spectrum of action, to extend the duration of action, to increase the rate of action, to prevent repellence or to prevent development of resistance.
  • such combinations may enhance plant growth, increase tolerance to high or low temperatures, to dryness or to water or soil salinity, to increase flowering efficiency, to facilitate harvesting and to increase crop yields, to enhance maturity, quality and / or nutritional value increase crop yield, extend shelf life, and / or improve crop workability.
  • synergistic effects are obtained by combining the active compounds according to the invention and the mixing partners, ie the effectiveness of the particular mixture is greater than the effectiveness of the individual components.
  • the combinations can be used both as seed applications and in pre-tank, tank or finished mixtures.
  • Particularly favorable mixing partners are e.g. the following
  • drugs with unknown mechanism of action such as azadirachtin, amidoflumet, benzoximate, bifenazate, quinomethionate, cryolites, cyflumetofen, dicofol, fluensulfone (5-chloro-2 - [(3,4,4-trifluorobut-3-en-1-yl) sulfonyl] -1,3-thiazoles), flufenerim, pyridalyl and pyrifluquinazone; furthermore preparations based on Bacillus firmus (I-1582, BioNeem, Votivo) and the following known active compounds
  • a penetration enhancer is additionally added to the plant protection products to increase the effect.
  • suitable penetration promoters are substances which promote the availability of the compounds of the formula (I) in the spray coating. These include, for example, mineral or vegetable oils. Suitable oils are all mineral or vegetable, optionally modified, oils which can usually be used in agrochemical compositions. Examples include sunflower oil, rapeseed oil, olive oil, castor oil, rapeseed oil, corn kernel oil, cottonseed oil and soybean oil or the esters of said oils. Preference is given to rapeseed oil, sunflower oil and their methyl or ethyl esters, in particular rapeseed oil methyl ester.
  • the concentration of penetration promoter can be varied within a wide range in the agents according to the invention.
  • a formulated crop protection agent it is generally from 1 to 95% by weight, preferably from 1 to 55% by weight, more preferably from 15 to 40% by weight.
  • the concentration is generally between 0.1 and 10 g / l, preferably between 0.5 and 5 g / l.
  • the active compounds according to the invention can furthermore be present in the form of insecticides in their commercial formulations and in the formulations prepared from these formulations in admixture with synergists.
  • Synergists are compounds which increase the effect of the active ingredients without the added synergist itself having to be active.
  • the active compounds according to the invention may furthermore, when used as insecticides in their commercial formulations and in the forms of use prepared from these formulations, be present in mixtures with inhibitors which reduce degradation of the active ingredient after application in the environment of the plant, on the surface of plant parts or in plant tissues ,
  • the active substance content of the application forms prepared from the commercial formulations can vary within wide ranges.
  • the active ingredient concentration of the use forms may be from 0.00000001 up to 95% by weight of active compound, preferably between 0.00001 and 1% by weight.
  • the application is done in a custom forms adapted to the application.
  • plants and parts of plants can be treated.
  • plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or can not be protected by plant breeders' rights.
  • Plant parts are to be understood as meaning all aboveground and underground parts and organs of the plants, such as shoot, leaf, flower and root, by way of example leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds and roots, tubers and rhizomes.
  • the plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.
  • the treatment according to the invention of the plants and plant parts with the active ingredients takes place directly or by acting on their environment, habitat or storage space according to the customary treatment methods, eg by dipping, spraying, evaporating, atomizing, spreading, brushing on, Injecting and propagating material, in particular seed, continue by single or multi-layer wrapping.
  • plants and their parts can be treated.
  • wild-type or plant species obtained by conventional biological breeding methods such as crossing or protoplast fusion
  • plant cultivars and their parts are treated.
  • transgenic plants and plant cultivars obtained by genetic engineering if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated.
  • the terms "parts” or “parts of plants” or “plant parts” have been explained above.
  • Plant varieties are understood as meaning plants having new traits which have been bred by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, biotypes and genotypes.
  • the treatment according to the invention may also give rise to superadditive ("synergistic") effects.
  • superadditive for example, reduced application rates and / or extensions of the spectrum of action and / or an increase in the effect of the substances and agents used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering power facilitated harvest, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or machinability of the harvested products, which exceed the actual expected effects.
  • the preferred plants or plant varieties to be treated according to the invention to be treated include all plants which, as a result of the genetic engineering modification, obtained genetic material which gives these plants particularly advantageous valuable properties ("traits").
  • traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to bottoms salt, increased flowering, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products , higher shelf life and / or workability of the harvested products.
  • Further and particularly highlighted examples of such properties are one increased defense of the plants against animal and microbial pests, such as insects, mites, phytopathogenic fungi, bacteria and / or viruses and increased tolerance of the plants against certain herbicidal active ingredients.
  • transgenic plants are the important crops such as cereals (wheat, rice), corn, soybeans, potatoes, sugar beets, tomatoes, peas and other vegetables, cotton, tobacco, oilseed rape and fruit plants (with the fruits apples, pears, citrus fruits and Grapes), with special emphasis on maize, soya, potato, cotton, tobacco and oilseed rape.
  • Traits which are particularly emphasized are the increased defense of the plants against insects, arachnids, nematodes and snails by toxins which are formed in the plants, in particular those which are produced by the genetic material from Bacillus thuringiensis (for example by the genes CryIA (a) , CryIA (b), CryIA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and their combinations) in the plants (hereinafter "Bt plants”).
  • Traits also highlight the increased resistance of plants to fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits which are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (eg "PAT" gene). The genes which confer the desired properties (“traits”) can also occur in combinations with one another in the transgenic plants.
  • SAR systemic acquired resistance
  • PAT phosphinotricin
  • Bt plants are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD GARD ® (for example maize, cotton, soya beans), KnockOut ® (for example maize), StarLink ® (for example maize), Bollgard ® ( cotton), NuCOTN ® (cotton) and NewLeaf ® (potato).
  • herbicide-tolerant plants are maize varieties, cotton varieties and soybean varieties may be mentioned, under the trade names Roundup Ready ® (tolerance to glyphosate, for example maize, cotton, soya bean), Liberty Link ® (tolerance to phosphinotricin, for example oilseed rape), IMI ® (tolerance against imidazolinone) and STS® (tolerance to sulfonylureas eg corn).
  • Roundup Ready ® tolerance to glyphosate, for example maize, cotton, soya bean
  • Liberty Link ® tolerance to phosphinotricin, for example oilseed rape
  • IMI ® tolerance against imidazolinone
  • STS® tolerance to sulfonylureas eg corn
  • Clearfield ® varieties eg corn
  • the listed plants can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the active substance mixtures according to the invention.
  • the preferred ranges given above for the active compounds or mixtures also apply to the treatment of these plants. Particularly emphasized is the plant treatment with the compounds or mixtures specifically mentioned in the present text.
  • the present invention therefore more particularly relates to a method of protecting seed and germinating plants from attack by pests by treating the seed with a compound of formula (I).
  • the method according to the invention for the protection of seeds and germinating plants from infestation by pests comprises a method in which the seed is treated simultaneously in one operation with an active ingredient of the formula (I) and one or more mixing partners. It also includes a method in which the seed is treated at different times with an active ingredient of the formula (I) and one or more mixing partners.
  • the invention also relates to the use of compounds of formula (I) for the treatment of seed for the protection of the seed and the resulting plant from animal pests.
  • the invention relates to seed which has been treated for protection against animal pests with a compound of formula (I).
  • the invention also relates to seed treated at the same time with an active ingredient of the formula (I) and one or more mixing partners.
  • the invention further relates to seed which has been treated at different times with an active compound of the formula (I) and one or more mixing partners.
  • the individual active substances of the agent according to the invention may be present in different layers on the seed. In this case, the layers containing an active ingredient of the formula (I) and the one or more mixing partners may be separated by an intermediate layer.
  • the invention also relates to seed, in which an active ingredient of the formula (I) and the or the mixing partner as Part of an envelope or as a further layer or further layers are applied in addition to a sheath.
  • the invention relates to seed which, after treatment with a compound of the formula (I), is subjected to a film coating process in order to avoid dust abrasion on the seed.
  • One of the advantages of the present invention is that because of the particular systemic properties of the compositions of the invention, treatment of the seeds with these agents not only protects the seed itself but also the resulting plants after emergence from animal pests. In this way, the immediate treatment of the culture at the time of sowing or shortly afterwards can be omitted.
  • Another advantage is the fact that by treating the seed with a compound of formula (I) germination and emergence of the treated seed can be promoted.
  • compounds of the formula (I) can be used in combination with signal technology agents, by way of example a better colonization with symbionts, such as rhizobia, mycorrhiza and / or endophytic bacteria, takes place and / or it is an optimized one Nitrogen fixation is coming.
  • symbionts such as rhizobia, mycorrhiza and / or endophytic bacteria
  • compositions according to the invention are suitable for the protection of seeds of any plant variety used in agriculture, in the greenhouse, in forests or in horticulture.
  • these are seeds of cereals (eg wheat, barley, rye, millet and oats), corn, cotton, soy, rice, potatoes, sunflower, coffee, tobacco, canola, oilseed rape, turnip (eg sugar beet and Fodder beet), peanut, vegetables (eg tomato, cucumber, bean, cabbage, onions and lettuce), fruit plants, turf and ornamental plants.
  • cereals eg wheat, barley, rye and oats
  • corn, soya, cotton, canola, oilseed rape and rice are examples of seeds of cereals (eg wheat, barley, rye and oats), corn, soya, cotton, canola, oilseed rape and rice.
  • transgenic seed with a compound of the formula (I) is also of particular importance.
  • the heterologous genes in transgenic seed can come from microorganisms such as Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium.
  • the present invention is particularly suitable for the treatment of transgenic seed containing at least one heterologous gene derived from Bacillus sp. comes. Most preferably, this is a heterologous gene derived from Bacillus thuringiensis.
  • a compound of the formula (I) is applied to the seed alone or in a suitable formulation.
  • the seed is treated in a state where it is so stable that no damage occurs during the treatment.
  • the treatment of the seed can be done at any time between harvesting and sowing.
  • seed is used which has been separated from the plant and freed from flasks, shells, stems, hull, wool or pulp.
  • seed may be used which has been harvested, cleaned and dried to a moisture content below 15% by weight.
  • seed may also be used which, after drying, e.g. treated with water and then dried again.
  • the agents according to the invention can be applied directly, ie without containing further components and without being diluted.
  • suitable formulations and methods for seed treatment are known to the person skilled in the art and are described, for example, in the following documents: US 4,272,417 A . US 4,245,432 A . US 4,808,430 A . US 5,876,739 A . US 2003/0176428 A1 . WO 2002/080675 A1 . WO 2002/028186 A2 ,
  • the compounds of the formula (I) can be converted into the customary seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other seed coating compositions, and also ULV formulations.
  • formulations are prepared in a known manner by mixing the compounds of formula (I) with conventional additives, such as conventional extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, Gibberellins and also water.
  • conventional additives such as conventional extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, Gibberellins and also water.
  • Dyes which may be present in the seed dressing formulations which can be used according to the invention are all dyes customary for such purposes. There are both in Water sparingly soluble pigments as well as water-soluble dyes usable. Examples which may be mentioned are the dyes known under the names Rhodamine B, CI Pigment Red 112 and CI Solvent Red 1.
  • Suitable wetting agents which may be present in the seed dressing formulations which can be used according to the invention are all wetting-promoting substances customary for the formulation of agrochemical active compounds.
  • Preferably used are alkylnaphthalene sulfonates, such as diisopropyl or diisobutyl naphthalene sulfonates.
  • Suitable dispersants and / or emulsifiers which may be present in the seed dressing formulations which can be used according to the invention are all nonionic, anionic and cationic dispersants customary for the formulation of agrochemical active compounds.
  • Preferably usable are nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants.
  • Particularly suitable nonionic dispersants are, in particular, ethylene oxide-propylene oxide, block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ethers and their phosphated or sulfated derivatives.
  • Suitable anionic dispersants are in particular lignosulfonates, polyacrylic acid salts and arylsulfonate-formaldehyde condensates.
  • Defoamers which may be present in the seed-dressing formulations which can be used according to the invention are all foam-inhibiting substances customary for the formulation of agrochemical active compounds.
  • Preferably usable are silicone defoamers and magnesium stearate.
  • Preservatives which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Examples include dichlorophen and Benzylalkoholhemiformal.
  • Suitable secondary thickeners which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Preference is given to cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica.
  • Suitable adhesives which may be present in the seed dressing formulations which can be used according to the invention are all customary binders which can be used in pickling agents.
  • Preferably mentioned are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose.
  • the gibberellins are known (see. R. Wegler "Chemie der convinced- und Swdlingsbekungsstoff", Vol. 2, Springer Verlag, 1970, p. 401-412 ).
  • the seed dressing formulations which can be used according to the invention can be used either directly or after prior dilution with water for the treatment of seed of various kinds.
  • the concentrates or the preparations obtainable therefrom by dilution with water can be used for dressing the seeds of cereals such as wheat, barley, rye, oats and triticale, as well as the seeds of corn, rice, rape, peas, beans, cotton, sunflowers and beets or even vegetable seeds of various nature.
  • the seed dressing formulations which can be used according to the invention or their diluted preparations can also be used for pickling seeds of transgenic plants. In this case, additional synergistic effects may occur in interaction with the substances formed by expression.
  • the seed dressing formulations which can be used according to the invention or the preparations prepared therefrom by the addition of water
  • all mixing devices customarily usable for the dressing can be considered.
  • the seed is placed in a mixer which adds either desired amount of seed dressing formulations either as such or after prior dilution with water and mixes until evenly distributed the formulation on the seed.
  • a drying process follows.
  • the application rate of the seed dressing formulations which can be used according to the invention can be varied within a relatively wide range. It depends on the particular content of the active substance (s) in the formulations and on the seed.
  • the application rates of active ingredients or active compound combinations are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 15 g per kilogram of seed.
  • Trimenopon spp. Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.
  • Nematocerina and Brachycerina e.g. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp , Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Glossina spp., Chrysomyia spppp
  • heteropterid e.g. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
  • Actinedida Prostigmata
  • Acaridida e.g. Acarapis spp., Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp , Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.
  • the active compounds of the formula (I) according to the invention are also suitable for controlling arthropods, the livestock, such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalos, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as dogs, cats, caged birds, aquarium fish and so-called experimental animals, such as hamsters, guinea pigs, rats and mice infested.
  • livestock such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalos, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as dogs, cats, caged birds, aquarium fish and so-called experimental animals, such as hamsters, guinea pigs, rats and mice infested.
  • the use of the active compounds according to the invention is carried out in the veterinary sector and in animal husbandry in a known manner by enteral administration in the form of, for example, tablets, capsules, infusions, drenches, granules, pastes, boluses, the feed-through procedure, suppositories, by parenteral administration, as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, by nasal application, by dermal application in the form of, for example, diving or bathing (dipping), spraying, pouring (pour-on and spot-on ), washing, powdering and with the aid of active substance-containing moldings, such as collars, ear tags, tail marks, limb bands, holsters, marking devices, etc.
  • enteral administration in the form of, for example, tablets, capsules, infusions, drenches, granules, pastes, boluses, the feed-through procedure, suppositories
  • parenteral administration as
  • the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowable agents) which contain the active ingredients in an amount of from 1 to 80% by weight, directly or apply after 100 to 10,000 times dilution or use as a chemical bath.
  • formulations for example powders, emulsions, flowable agents
  • the compounds according to the invention show a high insecticidal activity against insects which destroy industrial materials.
  • Non-living materials such as preferably plastics, adhesives, glues, papers and cardboard, leather, wood, wood processing products and paints.
  • the ready-to-use agents may optionally contain further insecticides and optionally one or more fungicides.
  • the compounds according to the invention can be used to protect against fouling of objects, in particular hulls, sieves, nets, structures, quay systems and signal systems, which come into contact with seawater or brackish water.
  • the compounds according to the invention can be used alone or in combinations with other active substances as antifouling agents.
  • Acarina e.g. Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae.
  • Opiliones e.g. Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.
  • Diptera e.g. Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp., Stomoxys Calcitrans, Tipula paludosa.
  • Lepidoptera e.g. Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
  • Ctenocephalides canis Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
  • Hymenoptera e.g. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
  • Heteroptera e.g. Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.
  • the application is carried out in aerosols, non-pressurized sprays, eg pump and atomizer sprays, fog machines, foggers, foams, gels, evaporator products with evaporator plates
  • Cellulose or plastic liquid evaporators, gel and membrane evaporators, propeller driven evaporators, energyless or passive evaporation systems, moth papers, moth cakes and moth gels, as granules or dusts, in litter or bait stations.
  • the calibration is carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms), whose logP values are known (determination of the logP values by means of the retention times by linear interpolation between two consecutive alkanones).
  • the NMR spectra were determined on a Bruker Avance 400 equipped with a flow-through head (60 ⁇ l volume). In individual cases the NMR spectra were measured with a Bruker Avance II 600.
  • the NMR data of selected examples are listed in classical form ( ⁇ values, multiplet splitting, number of H atoms).
  • the splitting of the signals was described as follows: s (singlet), d (doublet), t (triplet), q (quartet), quint (quintuplet), m (multiplet), b (for broad signals).
  • the solvents used were CD 3 CN, CDCl 3 or D6-DMSO, tetramethylsilane (0.00 ppm) being used as reference.
  • Step 1 5-Amino-N-ethyl-1- (pyridin-3-yl) -1H-pyrazole-4-carboxamide (IIa-1-1)
  • Step 1 3-Amino-N-isopropyl-1- (pyridin-3-yl) -1H-pyrazole-4-carboxamide (IIb-1-2)
  • Step 1 3-Amino-N-ethyl-1- (pyridin-3-yl) -1H-pyrazole-4-carboxamide (IIb-1-1)
  • Step 1 3-Amino- N- isopropyl-1-pyridazin-4-yl-pyrazole-4-carboxamide (IIb-3-1)
  • N- dimethylacetamide 35 mg (0.20 mmol) of p- toluenesulfonic acid and 120 mg (0.81 mmol) of triethyl orthoformate.
  • the reaction mixture was heated to 140 ° C for 1 h at 200 watts in a CEM Discover microwave. After cooling, the reaction mixture was concentrated, taken up in a little saturated sodium bicarbonate solution and extracted three times with methylene chloride. The organic phases were separated, combined, dried over sodium sulfate, filtered and concentrated.
  • a first fraction contained 39 g of a mixture of 70% ethyl 5-amino-1- (pyridin-3-yl) - 1 H -pyrazole-4-carboxylate (IIIa-1) and 30% ethyl 3-amino-1- (pyridin-3-yl) - 1 H -pyrazole-4-carboxylate (IIIb-1), according to LC / MS.
  • a second fraction contained 10 g consisting of 83% ethyl 3-amino-1- (pyridin-3-yl) - 1 H -pyrazole-4-carboxylate (IIIb-1) by LC / MS. Separation of (IIIa-1) and (IIIb-1) from the first fraction by preparative HPLC afforded an additional 24.5 g (96% purity) of ethyl 5-amino-1- (pyridin-3-yl) -1H- pyrazole-4-carboxylate as formate (IIIa-1) and 11.5 g (99% purity) of ethyl 3-amino-1- (pyridin-3-yl) - 1 H -pyrazole-4-carboxylate (IIIb-1) , (IIIa-1) .HCOOH logP [a]: 1.18; logP [b]: 1.27; 1H-NMR (D6-DMSO, 400MHz) ⁇ ppm: 12.8 (bs, 1H), 8.78 (d,
  • the reaction mixture was brought to reflux temperature and stirred for a total of 7.5 h at about 150 ° C. After cooling, the reaction mixture was concentrated and the residue was purified by MPLC over an RP (C-18) column with acetonitrile / water.
  • the isolated fraction contained 2.97 g of a mixture of 90% ethyl 5-amino-1- (pyrimidin-5-yl) - 1 H -pyrazole-4-carboxylate (IIIa-2) and 9% of ethyl 3-amino- 1- (pyrimidin-5-yl) - 1 H -pyrazole-4-carboxylate (IIIb-2) by LC / MS.
  • the separation of the products was then carried out by preparative HPLC.
  • reaction mixture was brought to reflux temperature and stirred for a total of 7.5 h at about 150 ° C. After cooling, the reaction mixture was filtered, the filtrate was concentrated and the residue was purified by MPLC over RP (C-18) column with water / acetonitrile / 0.1% formic acid. The higher-content fractions were taken up in acetonitrile for re-separation, leaving an insoluble part behind. This was filtered off with suction and dried. 1.18 g (80% purity, 13% of theory) of ethyl 3-amino-1-pyridazin-4-yl-pyrazole-4-carboxylate (IIIb-3) were obtained.
  • the filtrate was applied to RP (C-18) material and purified by MPLC over RP (C-18) column with water / acetonitrile / 0.1% formic acid.
  • the isolated fraction contained 0.41 g of a mixture of 73% ethyl 5-amino-1-pyridazin-4-yl-pyrazole-4-carboxylate (IIIa-3) and 13% ethyl-3-amino-1-pyridazine- 4-yl-pyrazole-4-carboxylate (IIIb-3) according to LC / MS.
  • Myzus persicae - spray test Solvent: 78 parts by weight of acetone 1.5 parts by weight of dimethylformamide emulsifier: Alkylarylpolyglykolether
  • active compound 1 part by weight of active compound is dissolved with the stated parts by weight of solvent and filled with water containing an emulsifier concentration of 1000 ppm until reaching the desired concentration. To prepare further test concentrations, dilute with emulsifier-containing water.
  • Chinese cabbage leaf discs Brassica pekinensis ) infested with all stages of the green peach aphid ( Myzus persicae ) are sprayed with an active compound preparation of the desired concentration.
  • a suitable preparation of active compound 1 part by weight of active compound is dissolved with the stated parts by weight of solvent and filled with water containing an emulsifier concentration of 1000 ppm until reaching the desired concentration.
  • emulsifier concentration 1000 ppm until reaching the desired concentration.
  • dilute with emulsifier-containing water dilute with ammonium salts or / and penetration promoters they are added in each case in a concentration of 1000 ppm of the preparation solution.
  • Bell pepper plants Capsicum annuum
  • Myzus persicae green peach aphid
  • Vessels are filled with sand, drug solution, an egg larvae suspension of the southern root gallbladder ( Meloidogyne incognita) and lettuce seeds.
  • the lettuce seeds germinate and the plantlets develop.
  • the galls develop at the roots.
  • the nematicidal activity is determined on the basis of bile formation in%. 100% means that no bile was found; 0% means that the number of bile on the treated plants corresponds to the untreated control.

Claims (8)

  1. Utilisation non thérapeutique de composés de formule (I)
    Figure imgb0133
     dans laquelle
    Het représente un radical de la série
    Figure imgb0134
    Figure imgb0135
     dans laquelle la ligne en pointillés représente la liaison vers un des atomes d'azote dans le cycle pyrazole, et
    G1 représente N ou C-A1,
    A1 représente hydrogène, halogène, cyano, nitro, alkyle, halogénoalkyle, alcoxy, halogénoalcoxy, ou cycloalkyle ou cycloalcényle chacun éventuellement substitué,
    A2 représente hydrogène, halogène, cyano, nitro, alkyle, halogénoalkyle, alcoxy, halogénoalcoxy, ou cycloalkyle ou cycloalcényle chacun éventuellement substitué,
    R représente hydrogène, alkyle, halogénoalkyle ou cycloalkyle éventuellement substitué,
    R1 représente un radical de la série constituée par hydrogène, alkyle, halogénoalkyle, cyanoalkyle, alcényle, halogénoalcényle, alcynyle, halogénoalcynyle, alcoxy, halogénoalcoxy, alcoxyalkyle éventuellement substitué par halogène, bis(alcoxy)alkyle éventuellement substitué par halogène, alkylsulfanylalkyle éventuellement substitué par halogène, alkylcarbonylalkyle éventuellement substitué par halogène, alkylsulfinylalkyle éventuellement substitué par halogène, alkylsulfonylalkyle éventuellement substitué par halogène, dialkylaminosulfanylalkyle, dialkylaminosulfinylalkyle, dialkylaminosulfonylalkyle, alcoxycarbonylalkyle éventuellement substitué par halogène, alcynyloxy éventuellement substitué par halogène, alcynyloxycarbonyle éventuellement substitué par halogène, dialkylaminocarbonyle, N-alkyl-N-cycloalkylaminocarbonyle, dialkylaminocarbonylalkyle, N-alkyl-N-cycloalkylaminocarbonylalkyle, hétérocyclylcarbonylalkyle, alkylsulfanyle, halogénoalkylsulfanyle, alkylsulfinyle, halogénoalkylsulfinyle, alkylsulfonyle, halogénoalkylsulfonyle, cycloalkyle éventuellement substitué par halogène, cyano, nitro, alkyle, halogénoalkyle, alcoxy, halogénoalcoxy, alcoxycarbonyle, halogénoalcoxycarbonyle ou hétaryle (qui est éventuellement lui-même substitué par alkyle ou halogène), cycloalkylcarbonyle éventuellement substitué par halogène, cyano, alkyle, halogénoalkyle, alcoxy, halogénoalcoxy, alcoxycarbonyle, halogénalcoxycarbonyle ou hétaryle (qui est éventuellement lui-même substitué par alkyle ou halogène), cycloalkylalkyle éventuellement substitué par halogène, cyano, nitro, alkyle, halogénoalkyle, alcoxy, halogénoalcoxy, alcoxycarbonyle, halogénoalcoxycarbonyle ou hétaryle (qui est éventuellement lui-même substitué par alkyle ou halogène), hétérocyclyle éventuellement substitué, hétérocyclylalkyle éventuellement substitué par halogène, cyano (également dans la partie alkyle), nitro, alkyle, halogénoalkyle, cycloalkyle (qui peut être substitué), alcoxy, halogénoalcoxy, alkylthio, haloalkylthio, alkylsulfinyle, alkylsulfonyle, haloalkylsulfinyle, haloalkylsulfonyle, amino, alkylamino, dialkylamino, alkylcarbonylamino, alcoxycarbonylamino, alcoxyalkyle, halogénoalcoxyalkyle, alcényle, alcynyle, cycloalkylalkyle, alkylcarbonyle, alcoxycarbonyle ou aminocarbonyle, aryle éventuellement substitué par halogène, cyano, nitro, alkyle, halogénoalkyle, cycloalkyle (qui peut être substitué), alcoxy ou halogénoalcoxy, arylalkyle éventuellement substitué par halogène, cyano, alkyle, halogénoalkyle, cycloalkyle (qui peut être substitué), alcoxy ou halogénoalcoxy, hétaryle éventuellement substitué par halogène, cyano (également dans la partie alkyle), nitro, alkyle, halogénoalkyle, cycloalkyle (qui peut être substitué), alcoxy, halogénoalcoxy, alkylthio, haloalkylthio, alkylsulfinyle, alkylsulfonyle, haloalkylsulfinyle, haloalkylsulfonyle, amino, alkylamino, dialkylamino, alkylcarbonylamino, alcoxycarbonylamino, alcoxyalkyle, halogénoalcoxyalkyle, alcényle, alcynyle, cycloalkylalkyle, alkylcarbonyle, alcoxycarbonyle ou aminocarbonyle, hétarylalkyle éventuellement substitué par halogène, cyano (également dans la partie alkyle), nitro, alkyle, halogénoalkyle, cycloalkyle (qui peut être substitué), alcoxy, halogénoalcoxy, alkylthio, haloalkylthio, alkylsulfinyle, alkylsulfonyle, haloalkylsulfinyle, haloalkylsulfonyle, amino, alkylamino, dialkylamino, alkylcarbonylamino, alcoxycarbonylamino, alcoxyalkyle, halogénoalcoxyalkyle, alcényle, alcynyle, cycloalkylalkyle, alkylcarbonyle, alcoxycarbonyle ou aminocarbonyle,
    R2 représente hydrogène ou alkyle,
    Q représente azote ou C-R3,
    R3 représentant un radical de la série constituée par hydrogène, alkyle, halogénoalkyle, OH, alcoxy, halogénoalcoxy, SH, alkylsulfanyle, alkylsulfinyle, alkylsulfonyle, NH2, alkylamino et dialkylamino,
    V représente un radical de la série constituée par oxygène, soufre et NR4, et
    R4 représente un radical de la série constituée par hydrogène, cyano, alkyle, halogénoalkyle et cycloalkyle,
    pour lutter contre des animaux nuisibles.
  2. Composés de formule (Ia)
    Figure imgb0136
     dans laquelle
    Het représente un radical de la série
    Figure imgb0137
    Figure imgb0138
     dans laquelle la ligne en pointillés représente la liaison vers l'atome d'azote dans le cycle pyrazole, et
    G1 représente N ou C-A1,
    A1 représente hydrogène, halogène, cyano, nitro, alkyle, halogénoalkyle, alcoxy, halogénoalcoxy, ou cycloalkyle ou cycloalcényle éventuellement substitué,
    A2 représente hydrogène, halogène, cyano, nitro, alkyle, halogénoalkyle, alcoxy, halogénoalcoxy, ou cycloalkyle ou cycloalcényle éventuellement substitué,
    R représente hydrogène, alkyle, halogénoalkyle ou cycloalkyle éventuellement substitué,
    R1 représente un radical de la série constituée par alkyle, halogénoalkyle, cyanoalkyle, alcényle, halogénoalcényle, alcynyle, halogénoalcynyle, alcoxy, halogénoalcoxy, alcoxyalkyle éventuellement substitué par halogène, bis(alcoxy)alkyle éventuellement substitué par halogène, alkylthioalkyle éventuellement substitué par halogène, alkylcarbonylalkyle éventuellement substitué par halogène, alkylsulfinylalkyle éventuellement substitué par halogène, alkylsulfonylalkyle éventuellement substitué par halogène, dialkylaminosulfanylalkyle, dialkylaminosulfinylalkyle, dialkylaminosulfonylalkyle, cycloalkyle éventuellement substitué par halogène, cyano, nitro, alkyle, halogénoalkyle, alcoxy, halogénoalcoxy, alcoxycarbonyle, halogénoalcoxycarbonyle ou hétaryle (qui est éventuellement lui-même substitué par alkyle ou halogène), cycloalkylalkyle éventuellement substitué par halogène, cyano, nitro, alkyle, halogénoalkyle, alcoxy, halogénoalcoxy, alcoxycarbonyle, halogénoalcoxycarbonyle ou hétaryle (qui est éventuellement lui-même substitué par alkyle ou halogène), hétérocyclyle éventuellement substitué, hétérocyclylalkyle éventuellement substitué par halogène, cyano (également dans la partie alkyle), nitro, alkyle, halogénoalkyle, cycloalkyle (qui peut être substitué), alcoxy, halogénoalcoxy, alkylthio, haloalkylthio, alkylsulfinyle, alkylsulfonyle, haloalkylsulfinyle, haloalkylsulfonyle, amino, alkylamino, dialkylamino, alkylcarbonylamino, alcoxycarbonylamino, alcoxyalkyle, halogénoalcoxyalkyle, alcényle, alcynyle, cycloalkylalkyle, alkylcarbonyle, alcoxycarbonyle ou aminocarbonyle, aryle éventuellement substitué par halogène, cyano, nitro, alkyle, halogénoalkyle, cycloalkyle (qui peut être substitué), alcoxy ou halogénoalcoxy, arylalkyle éventuellement substitué par halogène, cyano, alkyle, halogénoalkyle, cycloalkyle (qui peut être substitué), alcoxy ou halogénoalcoxy, hétaryle éventuellement substitué par halogène, cyano (également dans la partie alkyle), nitro, alkyle, halogénoalkyle, cycloalkyle (qui peut être substitué), alcoxy, halogénoalcoxy, alkylthio, haloalkylthio, alkylsulfinyle, alkylsulfonyle, haloalkylsulfinyle, haloalkylsulfonyle, amino, alkylamino, dialkylamino, alkylcarbonylamino, alcoxycarbonylamino, alcoxyalkyle, halogénoalcoxyalkyle, alcényle, alcynyle, cycloalkylalkyle, alkylcarbonyle, alcoxycarbonyle ou aminocarbonyle, hétarylalkyle éventuellement substitué par halogène, cyano (également dans la partie alkyle), nitro, alkyle, halogénoalkyle, cycloalkyle (qui peut être substitué), alcoxy, halogénoalcoxy, alkylthio, haloalkylthio, alkylsulfinyle, alkylsulfonyle, haloalkylsulfinyle, haloalkylsulfonyle, amino, alkylamino, dialkylamino, alkylcarbonylamino, alcoxycarbonylamino, alcoxyalkyle, halogénoalcoxyalkyle, alcényle, alcynyle, cycloalkylalkyle, alkylcarbonyle, alcoxycarbonyle ou aminocarbonyle,
    R2 représente hydrogène ou alkyle,
    Q représente azote ou C-R3,
    R3 représentant un radical de la série constituée par hydrogène, alkyle, halogénoalkyle, OH, alcoxy, halogénoalcoxy, SH, alkylsulfanyle, alkylsulfinyle, alkylsulfonyle, NH2, alkylamino et dialkylamino,
    V représente un radical de la série constituée par oxygène, soufre et NR4, et
    R4 représente un radical de la série constituée par hydrogène, cyano, alkyle, halogénoalkyle et cycloalkyle,
    à condition que les composés dans lesquels R1 représente 4-chlorophényle et simultanément Q représente C, R3 représente méthyle, V représente O, G1 représente N ou C-A1, et A1 et A2 représentent H soient exclus, et que les composés dans lesquels R1 représente 3-chlorophényle ou cycloalkyle éventuellement substitué et simultanément Q représente C-R3, R3 représente hydrogène et V représente O soient également exclus.
  3. Composés de formule (Ib)
    Figure imgb0139
     dans laquelle
    Het représente un radical de la série
    Figure imgb0140
    Figure imgb0141
     dans laquelle la ligne en pointillés représente la liaison vers l'atome d'azote dans le cycle pyrazole, et
    G1 représente N ou C-A1,
    A1 représente hydrogène, halogène, cyano, nitro, alkyle, halogénoalkyle, alcoxy, halogénoalcoxy, ou cycloalkyle ou cycloalcényle chacun éventuellement substitué,
    A2 représente hydrogène, halogène, cyano, nitro, alkyle, halogénoalkyle, alcoxy, halogénoalcoxy, ou cycloalkyle ou cycloalcényle chacun éventuellement substitué,
    R représente hydrogène, alkyle, halogénoalkyle ou cycloalkyle éventuellement substitué,
    R1 représente un radical de la série constituée par alkyle, halogénoalkyle, cyanoalkyle, alcényle, halogénoalcényle, alcynyle, halogénoalcynyle, alcoxy, halogénoalcoxy, alcoxyalkyle éventuellement substitué par halogène, bis(alcoxy)alkyle éventuellement substitué par halogène, alkylthioalkyle éventuellement substitué par halogène, alkylcarbonylalkyle éventuellement substitué par halogène, alkylsulfinylalkyle éventuellement substitué par halogène, alkylsulfonylalkyle éventuellement substitué par halogène, dialkylaminosulfanylalkyle, dialkylaminosulfinylalkyle, dialkylaminosulfonylalkyle, cycloalkyle éventuellement substitué par halogène, cyano, nitro, alkyle, halogénoalkyle, alcoxy, halogénoalcoxy, alcoxycarbonyle, halogénoalcoxycarbonyle ou hétaryle (qui est éventuellement lui-même substitué par alkyle ou halogène), cycloalkylalkyle éventuellement substitué par halogène, cyano, nitro, alkyle, halogénoalkyle, alcoxy, halogénoalcoxy, alcoxycarbonyle, halogénoalcoxycarbonyle ou hétaryle (qui est éventuellement lui-même substitué par alkyle ou halogène), hétérocyclyle éventuellement substitué, hétérocyclylalkyle éventuellement substitué par halogène, cyano (également dans la partie alkyle), nitro, alkyle, halogénoalkyle, cycloalkyle (qui peut être substitué), alcoxy, halogénoalcoxy, alkylthio, haloalkylthio, alkylsulfinyle, alkylsulfonyle, haloalkylsulfinyle, haloalkylsulfonyle, amino, alkylamino, dialkylamino, alkylcarbonylamino, alcoxycarbonylamino, alcoxyalkyle, halogénoalcoxyalkyle, alcényle, alcynyle, cycloalkylalkyle, alkylcarbonyle, alcoxycarbonyle ou aminocarbonyle, aryle éventuellement substitué par halogène, cyano, nitro, alkyle, halogénoalkyle, cycloalkyle (qui peut être substitué), alcoxy ou halogénoalcoxy, arylalkyle éventuellement substitué par halogène, cyano, alkyle, halogénoalkyle, cycloalkyle (qui peut être substitué), alcoxy ou halogénoalcoxy, hétaryle éventuellement substitué par halogène, cyano (également dans la partie alkyle), nitro, alkyle, halogénoalkyle, cycloalkyle (qui peut être substitué), alcoxy, halogénoalcoxy, alkylthio, haloalkylthio, alkylsulfinyle, alkylsulfonyle, haloalkylsulfinyle, haloalkylsulfonyle, amino, alkylamino, dialkylamino, alkylcarbonylamino, alcoxycarbonylamino, alcoxyalkyle, halogénoalcoxyalkyle, alcényle, alcynyle, cycloalkylalkyle, alkylcarbonyle, alcoxycarbonyle ou aminocarbonyle, hétarylalkyle éventuellement substitué par halogène, cyano (également dans la partie alkyle), nitro, alkyle, halogénoalkyle, cycloalkyle (qui peut être substitué), alcoxy, halogénoalcoxy, alkylthio, haloalkylthio, alkylsulfinyle, alkylsulfonyle, haloalkylsulfinyle, haloalkylsulfonyle, amino, alkylamino, dialkylamino, alkylcarbonylamino, alcoxycarbonylamino, alcoxyalkyle, halogénoalcoxyalkyle, alcényle, alcynyle, cycloalkylalkyle, alkylcarbonyle, alcoxycarbonyle ou aminocarbonyle,
    R2 représente hydrogène ou alkyle,
    Q représente azote ou C-R3,
    R3 représentant un radical de la série constituée par hydrogène, alkyle, halogénoalkyle, OH, alcoxy, halogénoalcoxy, SH, alkylsulfanyle, alkylsulfinyle, alkylsulfonyle, NH2, alkylamino et dialkylamino,
    V représente un radical de la série constituée par oxygène, soufre et NR4, et
    R4 représente un radical de la série constituée par hydrogène, cyano, alkyle, halogénoalkyle et cycloalkyle,
    à condition que les composés dans lesquels R1 représente phényle ou 4-chlorophényle et simultanément Q représente C, R3 représente méthyle, V représente O, G1 représente N ou C-A1, et A1 et A2 représentent H soient exclus.
  4. Agent, caractérisé par une teneur en au moins un composé de formule (I) selon la revendication 1 et des extendeurs et/ou substances tensioactives usuels.
  5. Agent, caractérisé par une teneur en au moins un composé de formule (Ia) selon la revendication 2 et des extendeurs et/ou substances tensioactives usuels.
  6. Agent, caractérisé par une teneur en au moins un composé de formule (Ib) selon la revendication 3 et des extendeurs et/ou substances tensioactives usuels.
  7. Utilisation non thérapeutique de composés de formule (Ia) selon la revendication 2 ou d'agents selon la revendication 5 pour lutter contre des nuisibles.
  8. Utilisation non thérapeutique de composés de formule (Ib) selon la revendication 3 ou d'agents selon la revendication 6 pour lutter contre des nuisibles.
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